Treatment of soya bean oil



Patented Sept. 6, was

UNlTED STATES 2,128,926 murmur or som BEAN on.

Albert K- Ep tein,

Application April 15, 193i,

No Drawing.

I Serial Chicago, Hi.

as on (Cl. zoo-42c) My invention relates to the treatment oi certain types'oi oils, especially soya bean oil, and is particularly concerned with improving the quality thereof whereby its utility in the field oi edible It has been known ior some considerable time that edible soya bean oil, including edible soya bean oil which has been refined, bleached and deodorized under the best 10 methods, undergoes a type of hich is characterized as reversion when exposed to light and air and, even though somewhat more slowly, when stored in the absence of light and air. in an acquisisometimes described as which subsequently often become intensialtered with the production of other undesirable flavors described as "oleo and or fishy. This type of spoilage is characteristic of soya bean oil. Even when edible, refined, bleached and deodorize'd soya bean oil is subjected to hydrogenation to produce a product having a melting point of from about 95 F. to 100 F., said partially verts, particularly after a few days and acquires an which becomes intensified with time. Even when the oil is kept in the dark,

, iood industries, such as in salad oil and particularly in plastic shortenings and in marga e. in the manufacture of margarine especially, reversion takes place relatively more quicklybecause 'oi the presence of moisture and othersubstances. while there is a decided advantage from an economic standpoint to employ soya bean oil in the food indusoi the abundance and and availability of such oil, neverbiems encountered tered in utilizing-this oil-in the I have acted as definite deterrents to the stimulation of such uses of soya bean oil.

I have discovered that, by treating soya. bean oil with certain reagents in certain proportions and under proper temperature and pressure conditions products are obtained which keep in good condition without reversion for periods or time substantially in excess the time before reverthe treatment or my invenactical effect of this treatment is that the commercial utility of soya bean oil in the is tremendously increased.

The improvement in the soya bean oil by reason or my treatment thereof manifests itself also in other respects, the most notable of which apso pears to lie in the reduction of color oi the treated sell. with (substantially 5 oxidizing gas serves oil. As will be pointed out more iully hereinafter, in some instances this reduction in color is very substantial.

It'is accordingly an object oi my invention to improve soya bean oil, particularly to enhance its utility for use in iood products. v

Another object of my invention concerns it extending the stability oi oi soya bean oil.

pics-reversion period resides in Still another object of my invention reducing the color oi soya bean oil.

other object of my invention deals with the provision of a novel method of treating soya bean oil to improve the same, with reference to extending or prolonging the period pre ceding reversion or, in other words, the pro-reversion period.

invention is the provision of a novel soya bean oil possessing the property periods of time without Another invention is conthod oi cerned with the development of a me treating soya bean oil to improve the same, especially with regard to extending the period preceding reversion, which method may easily be combined and coordinated with present practices in the art oi treating edible oils and fats, particulariv with respect to the res: g thereoi.

with these objects in view and others which will appear as the nature clear in the light oi the shall address ous phases oi my invention.

in general, my invention is discovery that when phosphoric predicated on the acid esters are added in very small amounts to soye bean oil and the oil is subjected to elevated temperatures, particularly under reduced pressures, i ence of steam or other non-oxidizing vapor or nitrogen or hydrogen, the resulting oil possesses new properties; lts'pre-reversion period is substantally prolonged and it undergoes a definite reduction in color. The steam or nonto sweep out the volatile constituents oi the oil undergoing treatment.

At this point,

invention from denced, for example, by Eckey and Albert S. Richardson et 1,993,152 and 1,993,181.

these patents is concerned with retarding the oxidation fats and oieaginous materials generally, oil being mentioned specifically, by the addition thereto ot'relatively small proportions of phosphoric acids and certain esters thereoi. My invention is not to be confused therewith. In the first place my process is concerned with the treatement oi soya been 011" which, by contrast with edible oils generally,

certain knownpractices as evial., numbered,

myself toiuliy explaining the vari- Each of I the patents to Eddy W.

phoric acid ester be treated in an non-oxidizing of Benjamin R Harris, Serial No. 10 atmosphere such as steam nitrogen, carbon di- 56,724 filed December 30 1935, and Serial No oxide or the like, particularly under reduced 12 ,272, flied February 11 1937. In order that pressure, and at temperatures of the order of those skilled in the art may better understand those employed in edible oil deodorization commy invention without the necessity of referring to mercial processes, namely, about 420 F. to the copending applications of Benjamin R Har- 15 500 preferably at the higher temperatures ris, referred to hereinabove, the following exam- Under hese conditions, a reaction takes place bepics are given by way of illustration of methods tween some of the constituents of the soya bean of preparing said special esters Reference, how- 011 and the phosphoric acid ester and it is my ever, may so be h d o he pa t0 en in belief that it is this reaction product which forms rris, No. 2,025,986, wherein such special 20 at the elevated temperatures which is responsible esters are shown for use in confection compofor the prolongation of the good flavor and resitions Example I tar-ds the development of the so-called beany or fishy fiavor in the soya bean oil The use Preparation -S 'X- hundred (600) of elevated temperatures also serves, with the pounds of cottonseed oil hydrogenated to an 25 steam or other non-oxidizing gas, to deodorize iodine value of about 69 and pounds of northe bean oil and to volatilize any undesirable con mally hquid cottonseed oil are heated together stituents formed by the interaction of the phoswith 250 pounds of glycerine to about 200 degree phoric acid ester and some of the constituents F. without stirring Twelve (12) ounces of soof said oil Although I have not yet fully ascerdium hydroxide fiakes are added and the tem- 3O tamed the mechanism of the reaction which takes perature raised to 485 degrees F. and held at place and appears to account for this unusual and that temperature for two hours with stirring unexpected retardation of the development of A non-oxidizing atmosphere, such as 001-, is eany or specific oif-fiavors in the treated soya maintained during the heatingand the cooling bean o it is my present theory that the phosto about 200 degrees F On standing glycerine 3 phone acid ester reacts with the ooniugated separates out and is removed. Glycerine still double bonds of t e coloring matter, such as suspended may be centrifuged out. The resultcarotene, present in the soya, bean oil I postuing product contains a mixture of monoand late this theory because, in general simultanedi-glycerides of the fatty acids present in the ously with the improvement of the keeping prophydrogenated cottonseed and normally liquid 40 erties or prolongation of the pre-reversion period cottonseed oils. of the soya bean oil, there is also a bleaching Pre-trea tment with PzO5.Sevenhundred (700) effect pon or reduction of color of said 011 pounds of the ester obtained in accordance with ile I am not to be bound by any theoretical the above process are transferred to a jacketed considerations, I have ofiered the same as a poskettle. Seventy-five (75) pounds of finely divided 45 sible explanation of why I obtain the results P205 are added at a temperature of F. with which I have already generally described and thorough agitation. The temperature rises to which will be more fully detailed hereinafter about 200 to 210 F. Steam is then-circulated At any rate, that a reaction takes place under in the jacket to raise the temperature to 240 F. the Conditions f my t atm n Can ot be gainand the mass is maintained at that temperature 50 said since the mere addition of the phosphoric for one-half hour with constant agitation The acid esters to soya bean oil does not serve to reaction product is then centrifuged to remove r n r x d th pr r v mi n p ri therethe P205 and adhering organic matter (about 150 of to any noticeable or appreciable extent. The pounds of a very viscous brown mass are cenphosphoric acid esters used at the high temtrifuged out, practically no P205 enters into 55 peratures under the conditions specified appear chemical combination with the ester in this preto exert a catalytic eflect with a resultant marked treatment stage). mp o m nt of the soya bean oi Esterz'flcation with PzO5.The clear liquid obe phosphoric acid esters'whi h Imay utilize tained in the pretreatment step is transferred are Varied and Include y yl Phosphoric acid back to the kettle and cooled to about 155 F. 0 and many other phosphoric acid esters includ- Seventy-five (75) pounds of finely divided P205 ing those disclosed in the patents to Benjamin are then added with agitation. At the same time Harris, Nos. 2,026 785 and 2 052,029 These cold water is circulated in the jacket The temcompounds are, in general, phosphoric acid esters perature rises to about 180 F. to F. in about of relatively high molecular weight alkyl or acyl five to ten minutes, remains at that temperature 1 derivatives of polyhydroxy substances Of exfor several minutes, and then begins to cool. It ceptional utility for my present purposes are the is then allowed to cool to about 150 F. The special types of phosphoric acid esters prepared total time required from the time the P205 is y a "pretreatment process followed by an esadded to when it reached maximum temperature terification reaction to produce esters of phosand is allowed to cool to 150 F. is about one-half 7 hour. This is the case when fine P205 is used. If coarse P205 is used, it is added at 160 F. The temperature rises slowly to 210 F. over a period of twenty minutes. There is then a tendency for the temperature to rise suddenly. This rise 7 pared from mono-glycerides, diglycerides, and

is checked by circulating cold water in the jacket.

The maximum temperature obtained in that way is about 214 F. to 215 F. and the reaction mixture remains at that temperature several minutes. It is then allowed to cool to about 150 F. This takes another twenty minutes. A dark reddish brown viscous liquid is thus obtained. If desired, the product may be neutralized as, for

,example, in the following manner:

Neutralization.-One-half of the reaction product is removed and the half remaining in the kettle is cooled to 120 F. Forty (40) pounds of finely divided anhydrous sodium carbonate are added at one time with continued agitation. The temperature may rise as high as 168 F. over a period of one-half hour. It should not be allowed to rise any higher. In most cases it goes up to about 160 F. It is then raised to 168 F. and kept at that temperature for about one-half hour, with continuous agitation. There is considerable efierverscence, but not as copious, violent or troublesome as when the pretreatment step is not used. The product is immediately centrifuged to-remove excess sodium carbonate.

Example II Substantially water free glycerine is polymerized, preferably with the aid of an alkali catalyst, until it has an average molecular weight corresponding to a diglyceroi. 166 parts of the polymerized product, 180 parts of oleic acid, and 105 parts of stearic acid of good commercial grade are mixed together and heated to a temperature of about 220 to 225 C. and maintained at that temperature for approximately two hours, the reaction mixture in the meantime being continuously stirred. Atmospheric oxygen is kept out of contact with the mixture, preferablyby maintaining an atmosphere of an inert gas at the surface, for example by bubbling carbon dioxide through the mixture continuously. The reaction should be allowed to continue until the acidity of the mixture is below 1%, the time, temperature and conditions described usually being suitable to produce this result. The product is then allowed to stand and any unreacted polyglycerol present is allowed to settle out.

To 450 parts of the mixed polyglycerol esters prepared as in the preceding paragraph, while at a temperature of approximately 60 C., 75 to parts of fine phosphorus pentoxide are slowly added. A jacketed vessel may be employed to control temperature. The product is heated to approximately C. and kept at that temperature for about twenty minutes. It is then removed from the vessel and centrifuged to remove insoluble materials, consisting for the most part of phosphorus pentoxide and adhering or loosely combined organic matter.

4100 parts of the pretreated product are returned to the jacketed vessel and at 50 C. ,fifty parts of fine phosphorus pentoxide are added slowly thereto. The reaction mixture is heated to about 70 C. and the temperature then rises to about 95 C. The product is kept at this temperature for a few minutes, the total time for the entire esterification step being about twenty-five minutes.

The esterified product, if neutralization is desired, is neutralized suitably either by the use of sodium carbonate, as described in Example I, or,

by the use of ammonia, or by employing any other suitable alkaline organic or inorganic neutralizing agent. In general, very good results are obtained ii the hydrogen ions of the hydrophile phosphate group are replaced by either sodium or ammonium ions.

Example III Pre-treatment.-450 parts of a product consisting essentially of mono-glycerides of cottonseed oil fatty acids were admixed with 120 parts of sodium bi-sulphate (NaHSOr), heated, with stirring, to about 120 degrees C., and kept at that temperature for about 20 minutes, the stirring being more or less continuous. When the stirring was stopped, a heavy, syrupy liquid collected rapidly at the bottom, leaving a clear supernatant liquid, the latter being separated by decantation.

Esterification.380 parts of the decanted liquid obtained above were mixed with 42 parts of finely divided P205 at about 50 degrees C. and the mix--, ture was heated, with stirring, to 105 degrees C. A reaction set in, the temperature rising to degrees C. The reaction mass was then allowed to cool.

(Note.The above process was also carried out in the same manner as described above except that, in the pre-treatment, in one instance '75 parts of sodium bi-sulphate and in another instance 38 parts of sodium oi-sulphate were employed. In each case it was necessary, in the subsequent reaction with P205 to raise the temperature higher than 105 degrees C. before a reaction set in. In the process in which 75 parts of sodium bi-sulphate were employed, it was necessary to raise the temperature to 125 degrees C. after which said temperature rose spontaneously to degrees C. In the process employing 38 parts of sodium bi-sulphate, even when the temperature was raised to degrees C. there was no spontaneous rise in temperature.)

Example IV Pre-treatment.450 parts of a diglyceride of a higher fatty acid were pre-treated with 60 parts of sodium-bi-sulphate at 125 degrees C. for approximately one-half hour. The mass was permitted to settle and a clear liquid decanted.

Esterification.380 parts of the decanted liquid were reacted with 40 parts of P205 at 50 degrees C. The mixture was heated to about 80 degrees C; after which the temperature spontaneously rose to about 90 degrees C. The reaction mass was then permitted to cool.

(Note.The diglyceride was prepared from a mixture of 200 parts of hydrogenated cottonseed oil having an iodine value of 67 and parts of corn oil, this mixture being heated in an atmosphere of CO2 with 110 parts-of glycerine and per cent sodium hydroxide (based on the weight of the oil) to 250 degrees C. and kept at that temperature for two hours.)

Generally speaking, crude soya bean oil, produced by the expeller process why the solvent process, contains a fraction of one per cent of free fatty acids, this, however, being variable. Such oil is refined in accordance with conventional processes involving neutralization of the free fatty acids with alkali or alkaline materials, removal of the resulting soap, drying, and bleaching with such agents as fullers earth or carbon black. The oil may then, if desired, bev hydrogenated in accordance with known practice to produce a product having a melting point of about 95 F. to 100 F. whereby it may be employed as a constituent of margarine or dry bakery shortenings. If desired, the hydrogenated soya bean oil may be washed again with a slight amount'of alkali and introduced into a deodorizing kettle-and deodorized with superheated steam under reduced pressure. f

I have found that I obtain excellent results with economy of-"treatrnent if the phosphoric acid esters in proper proportions are added to the soya been 011 just prior to the deodorization thereof with superheated steam under reduced pressure. .The. subjectiori"of the soya bean oil, admixed with the phosphoric acid esters, to these conditions of temperature and reduced. pressure produces a definite change in the oil in that some constituent or constituents of the soyabean' oil which cause or promote reversion become fixed and inactive while undesirable constituents formed or present become volatilized, thereby producing a product which keeps in good condition for relatively long periods of time without development of oleo-like or fishy or grassy flavors.

It must not be inferred that my process is limited to the treatment of hydrogenated soya bean oil or that the phosphoric acid esters must be introduced into the oil at any particular phase of the process of treatment or refining thereof. My process is also applicable to the treatment of liquid or non-hydrogenated soya bean oil. Furthermore, the phosphoric acid esters may be added at any suitable stage of the process of treating the soya bean oil. It is only necessary that the mixture of the soya bean oil and the phosphoric acid ester be subjected to a temperature sufliciently high to react, as, for example, about 400 vF. to 500 F. under reduced pressure for the requisite length of time, which will vary with the size of the batch undergoing treatment, generally a matter of one hour or several hours during which period the oil is also deodorized. While the soya bean oil admixed with the phosphoric acid ester could be subjected to the heat treatment in an inert or substantially non-oxidizing atmosphere, such as indicated above, followed by steam deodorization under reduced pressure at elevated temperatures ,-of the character described, I have found itto-be considerably more economical and somewhat better results are obtained if the treatment is effected as a part of and concomitant with the steam deodorization treatment to which the oils are subjected, the time being sufiiciently long, generally six or seven hours in large scale commercial operations, so as to drive 011' undesirable volatile constituents present in the oil or which might be formed in the reaction.

The following examples are illustrative of methods of practicing my invention. It will be understood, however, that said examples are given by way of illustration only and are not to be construed as limitative of the full scope of my invention as taughtherein.

Example A To a partially hydrogenated soya bean oil there was added 0.02% by weight of the phosphoric acid ester produced in accordance with Example I hereinabove and the mixture was heated with superheated steam for six hours at a temperature of 500 F. at an absolute pressure of -'1 mm. of mercury to remove undesired volatile constituents. In an accelerated test made by placing a sample of the oil thus treated in a bottle and exposing it to light, the oil kept in good condition for twelve days. A batch similarly treated but omitting the phosphoric acid ester and another batch similarly treated but utilizing 0.2% of said phosphoric acid ester kept only two days before reversion set in under the same accelerated test.

Example B Crude soya bean oil was refined in the conventional way by neutralization with alkali, re-

. moval of the resulting soap, drying and bleaching.

It was then mixed with 0.05% by weight of the phosphoric acid ester of Example 111 hereinabove and the mixture was heated at 490 degrees F. at a reduced absolute pressure of 9 mm. of mercury for a period of several hours until undesired volatile constituents were removed. In an accelerated test, as described in Example A, the oil thus treated has keeping qualities superior to a sample similarly treated but without the addition of the phosphoric acid ester.

' Example 0 five times as long as a sample similarly treated but without the addition of the phosphoric acid ester.

The proportions of phosphoric acid esters employed are quite critical. In general I have found that if substantially in excess of 0.5% of the phosphoric acid ester, based on the weight of the soya bean oil, is employed the results obtained are not quite so satisfactory as when small proportions are utilized. The proportions vary somewhat with particular soya bean oils, and, as a general rule, liquid soya bean oil requires greater proportions of the phosphoric acid esters than is required in the treatment of hydrogenated or partially hydrogenated soya bean oil. Thus, for example, in the case of a partially hydrogenated soya bean oil I have obtained relatively unsatisfactory results with as high as 0.3% of some of the phosphoric acid esters whereas 0.5% of the same phosphoric acid esters utilized in liquid or non-hydrogenated soya bean oil showed a fair prolongation of the prerevision period thereof. In general, bearing in mind the statements made above and the variability of different factors, including the extent of neutralization, as described below, I employ proportions ranging between about v0.0005% or 0.001% and 0.5% of the phosphoric acid esters, and preferably from 0.005 to 0.05%.

The phosphoric acid esters employed in my process are effective for my present purposes regardless of whether they are acid, neutral, or partially alkaline in reaction, it being understood, however, that they may differ somewhat in degree of eflicacy. In general, I prefer to employ the partially neutralized esters of phosphoric acids, those having a pH of about 5.5 having been found to give excellent results. As illustrative of the effect of pH of the phosphoric acid, ester upon the pre-reversion period of the soya bean oil, I call attention to the following results obtained in tests which I have conducted. Utilizing the phosphoric acid ester of Example I hereinabove,

the pH of which was from 5 to 5.5, accelerated tests on a partially hydrogenated soya bean oil treated in accordance with my process showed the,

oil to have good keeping properties for from twelve to sixteen days. All conditions being otherwise the same, the use of said phosphoric acid ester neutralized so as to have a pH of 7.1 produced an oil which kept in good condition under accelerated tests for six days. Under the same conditions, the same phosphoric acid ester neutralized to a pH of 8.4 kept the oil in good condition of eight days. The blank kept in good condition for two days. In each case, aside from the blank of course, 0.05% of the phosphoric acid ester was employed. In general, less of the non-neutralized phosphoric acid esters is necessary to obtain good results than of the neutralized or partially neutralized esters and in some cases an amount of a neutralized product which gives good results will, if substituted by the same amount of the non-neutralized product give relatively poor results. Thus, for example, I have obtained excellent results using as low as 0.0005% of the non-neutralized product of Example I but percentages of 0.5% of the same non-neutralized product gave relatively poor results. However, 0.5% of the neutralized product of Example I again gave satisfactory results. It will be understood that the term phosphoric acid ester is intended to cover the free acid ester as well as the partially neutralized or completely neutralized products unless otherwise specifically stated.

I have referred hereinabove to the temperatures which are utilized in my process. It is evident that any temperature, sufficiently high to effect the reaction between the phosphoric acid esters and the soya bean oil but not so high as to have an undesirable effect on the oil or to cause objectionable decomposition to take place, may be employed. I have stated that temperatures of 400 F. to 500 F. have proven satisfactory. Excellent results have been obtained at about 430 F. to 500 F. In general, to reiterate, the temperature must be high enough to volatilize, with the superheated steam or the like, the undersirable volatile constituents present in the oil and those which may be formed as reaction products.

The degree of vacuum utilized is, of course,

subject to variation. Excellent results have been obtained with absolute pressures of 7 to 15 mm. ofmercury but the operative range extends beyond either limit. In general, other things being equal, at low pressures the quality of the products obtained is an inverse function of the pressure, i. e., the lower the pressure, the better the product. i

As I have previously stated, concomitantly with the extension or prolongation of the pre-reversion period of the soya bean oil as a result of my treatment, there is, as a general rule, a reduction in color over and above that which is due to the steam deodorization treatment in those instances where I utilize my process in conjunction therewith. For example, with some partially hydrogenated soyabean oils having a melting point of about F., the color has been reduced by my treatment from about 13 Yellow and 1.3 Red (Lovibond scale) to from 4 to 3 Yellow and about 0.4 to 0.3 Red. In some cases of the treatment ofliquid soya bean oil, my process has reduced the color from 35 Yellow and 8 Red to 6 to '7 Yellow and 0.5 Red. I have found that some types of soya bean oil undergo somewhat of a bleaching or reduction in color during steam deodorization thereof when the phosphoric acid esters are not employed.. .How ever, such oils acquire a beany, fishy, grassy or oleo-like flavor relatively quickly. If, however, as I have described, the same oil is subjected to the same temperature and deodorization treatment but in the presence of the phosphoric acid esters incorporated therein prior to subjection to deodorization, there is an improvement not only in color but also in the keeping properties of the What I claim as new and desire to protect by Letters Patent of the United States is:

1. In a method of improving soya bean oil, particularly with respect to extending its pre-reversion period, the steps which comprise mixing said oil with not substantially in excess of 0.5% of a phosphoric acid ester, based on the weight of the oil, and heating the resulting mixture under reduced pressure at sufficiently high edible oil deodorization temperatures for a length of time suflicient to drive oir" undesirable constituents.

2. In a method of improving soya bean oil, particularly with respect to extending its pre-reversion period, the steps which comprise mixing said oil with between about 0.0005% and 0.5% of a phosphoric acid ester, based on the weight of the oil, and heating the resulting mixture under reduced pressure at a temperature between about 400 F. and 500 F. for a length of time sufficient to substantially deodorize the oil.

3. In a method of improving soya bean oil, particularly with respect to extending its pre-reversion period, the steps which comprise mixing said oil with not substantially in excess of 0.5% of a phosphoric acid ester, based on the weight of the oil, and heating the resulting mixture under reduced pressure and in the presence of superheated steam at edible oil deodorization temperatures for a length of time sufficient to substantially deodorize the oil.

4. In a method of improving soya bean oil, particularly with respect to extending its pre-reversion period, the steps which comprise mixing said oil with between about 0.0005% and 0.5% of a phosphoric acid ester, based on the weight of the oil, and heating the resulting mixture under reduced pressure and in the presence of superheated steam at edible oil deodorization temperatures for a length of time suflicient to substantially deodorize the oil.

5. The process of claim 1 wherein the phosphoric acid ester is a phosphoric acid ester of a polyhydroxy substance, the hydrogen of at least one hydroxy group of the polyhydroxy substance being replaced by a relatively long chain nonnitrogenous aliphatic lipophile radical.

6. The process of claim 2 wherein the phosphoric acid ester is a phosphoric acid ester of a polyhydroxy substance, the hydrogen of at least one hydroxy group of the polyhydroxy substance being replaced by a relatively long chain nonnitrogenous aliphatic lipophile radical.

7. The process of claim 3 wherein the phosphoric acid ester is a phosphoric acid ester of a polyhydroxy substance, the hydrogen of at least one hydroxy group-of the polyhydroxy substance being replaced by a relatively long chain nonnitrogenous aliphatic lipophile radical.

8. The process of claim 4 wherein the phosphoric acid ester is a phosphoric acid ester of a polyhydroxy substance, the hydrogen of at least one hydroxy group of the polyhydroxy substance being replaced by a relatively long chain nonnitrogenous aliphatic lipophile radical.

9. The process of claim 1 wherein the phosphoric acid ester is formed by pretreating a relatively high molecular weight acyl or .alkyl derivative of a polyhydroxy substance, having at least one free hydroxy group attached to the polyhy- ,droxy nucleus, with a member of the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, and then reacting the resulting product with a derivative of phosphorus capable of forming an ester of a phosphoric acid.

10. The process of claim 4 wherein the phosphoric acid ester is formed by pretreating a relatively high molecular weight acyl or alkyl derivative of a polyhydroxy substance, having at least one free hydroxy group attached to the polyhydroxy nucleus, with a member of the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, and then reacting the resulting product with a derivative of phosphorus capable of forming an ester of a phosphoric acid.

11. The process of claim 1 wherein the phosphoric acid ester is formed by pretreating fatty acid esters of glycerine containing at least one free glycerine hydroxy group and wherein the fatty acid radical contains between twelve and eighteen carbon atoms, said pretreating agent being selected from the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, then removing said pretreating agent and adhering material, and reacting the resulting pretreated product with phosphorus pentoxide.

12. The process of claim 4 wherein the phosphoric acid ester is formed by pretreating fatty acid esters of glycerine containing at least one free glycerine hydroxy group and wherein the fatty acid radical contains between twelve and eighteen carbon atoms, said pretreating agent being select-ed from the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, then removing said pretreating agent and adhering material, and reacting the resulting pretreated product with phosphorus pentoxide.

13. The process of claim 1 wherein the phosphoric acid ester is prepared from a mixture of monoglycerides and diglycerides resulting from the re-esterificati'on of cottonseed oil with glycerine, said ester being formed by pretreating said mixture of mono'glycerides and diglycerides with a member selected from the group consisting of phosphorous pentoxide, alkali metal bisulphates,

strong sulphuric acid,- sulphur trioxide, pyrosulphuric acid, and mixtures thereof, then removing said pretreating agent and adhering material, and reacting the resulting with phosphorous pentoxide.

14. The process of claim 4 wherein the phosphoric acid ester is prepared from a mixture of monoglycerides and diglycerides resulting from the re-esterification of cottonseed oil with glycerine, said esterbeing formed by pretreating said mixture of monoglycerides and diglycerides with a member selected from the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulpretreated product phuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, then removing said I pretreating agent and adhering material, and reacting the resulting pretreated produofi with phosphous pentoxide.

15. The process of claim 1 wherein the phosphoric acid ester is prepared by pretreating a higher fatty acid of glycerine containing at least one free glycerine hydroxy group with a minor proportion of a member selected from the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuricacid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, said pretreating step being carried out at a temperature of the order of 100 C. or higher, then removing said pretreating agent and adhering material, and reacting the resulting pretreated product with a relatively small proportion of phosphorus pentoxide at a temperature not substantially in excess of 100 c.

16. The process of claim 4 wherein the phosphoric acid ester is prepared by pretreating a higher fatty acid ester of glycerine containing at least one free glycerin hydroxy group with a minor proportion of a member selected from the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, said pretreating step being carried out at a temperature of the order of 100 C. or higher, then removing said pretreating agent and adhering material, and reacting the resulting pretreated product with a relatively small proportion of phosphorus pentoxide at a temperature not substantially in excess of 100 C.

17. The process of claim 1 wherein the soya bean oil, prior to treatment withthe phosphoric acid ester, has been at least partially refined and hydrogenated.

18. The process of claim 4 wherein the soya bean oil, prior to treatment with the phosphoric acid ester, has been at least partially'reflned and hydrogenated.

19. Soya bean oil, having an improved color and a substantially extended pre-reversion period, comprising the reaction product, under reduced pressure and at deodorization temperatures, of soya bean oil and not substantially in excess of 0.5% of a phosphoric acid ester based on the weight of said oil.

20. Soya bean oil, having an improved color and a substantially extended pre-reversion period, comprising the reaction product, under reduced pressure, in the presence of super-heated steam, and at deodorization temperatures, of soya bean oil and between about 0.0005% and 0.5% of a phosphoric acid ester based on the weight of said oil.

21. soya bean oil, having an improved color and a substantially extended pre-reversion period, comprising the reaction product, under reduced pressure and at deodorization temperatures, of soya bean oil and not substantially in excess of 0.5% of a phosphoric acid ester, based on the weight of said oil, wherein said ester is a phosphoric acid ester of a polyhydroxy substance, the hydrogen of at least one hydroxy group of said polyhydroxy substance being replaced by a relatively long chain non-nitrogenous aliphatic lipophile radical.

22. Soya bean oil, having an improved color and a substantially extended pre-reversion period and comprising the reaction product, under reduced pressure and at deodorization temperatures, of soya bean oil and not substantially in excess of 0.5% of a phosphoric acid ester, based on the weight of said oil, said phosphoric acid ester being formed by pretreating a relatively high molecular weight acyl or alkyl derivative of a polyhydroxy substance, having at least one free hydroxy group attached to the polyhydroxy nucleus, with a member or the group consisting of phosphorus pentoxide, alkali metal blsulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, and then reacting the resulting product with a derivative of phosphorus capable of forming an ester of a phosphoric acid.

23. Soya bean oil, having an improved color and a substantially extended pro-reversion period, comprising the reaction product, under reduced pressure and at deodorization temperatures, of soya bean oil and not substantially in excess of 0.5% of a phosphoric acid ester, based on the weight of said oil, said ester being formed by pretreating fatty acid esters of glycerine containing at least one free glycerine hydroxy group and wherein the fatty acid radical contains between twelve and eighteen carbon atoms, said pretreating agent being selected from the group consisting of phosphorus pentoxi-de, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, then re moving said pretreating agent and adhering material, and reacting the resulting pretreated prod not with. phosphorus pentoxide.

Z l. Soya bean oil, having an improved color and a substantially extended pre -reversion period, comprising the reaction product, underreduced pressure and at deodorization "temperatures, of soya bean oil and not substantially in excess of 0.5% of a phosphoric acid ester, based on the weight of said oil, said ester being prepared from a mixture of monoglycerides and diglycerides sulting from the re-esterification or cottonseed oil with glycerine, said. ester being formed by pretreating said mixture or mom lycerides and diriod, comprising the reaction product, under reduced pressure and at deodorization temperatures, of soya bean oil and not substantially in excess of 0.5% of a phosphoric acid ester, based on the weight of said oil, said ester being prepared by pretreating a higher fatty acid ester of glycerine containing at least one free glycerine hydroxy group with a minor proportion of a member selected from the group consisting of phosphorus pentoxide, alkali metal bisulphates, strong sulphuric acid, sulphur trioxide, pyrosulphuric acid, acid reacting salts of pyrosulphuric acid, and mixtures thereof, said pretreating step being carried out at a temperature of the order of C. or higher, then removing said pretreating agent and adhering material, and reacting the resulting pretreated product with a relatively small proportion of phosphorus pentoxide at a temperature not substantially in excess of 100 iii.

26. Partially hydrogenated soya bean oil, hav-- ing an improved color and a substantially ex-- tended pre-reversion period, comprising the action product, under reduced pressure and at deodorization temperatures, of soya bean oil not substantially in excess of 0.5% or a phosphoric acid ester, based on the weight of said oil.

27. Partially hydrogenated soya bean oil, having an improved color and a substantially extended pro-reversion period, comprising the reaction product, under reduced pressure, in the presence of super-heated steam, and at deodonzation temperatures, of soya bean oil and between about 0.0005% and 0.5% of a phosphoric acid ester, based on the weight of saidoil.

28. The method of improving soya bean oil, particularly with respect to extending its prereversion period, which comprises mixing said oil L with not substantially in excess of 0.5% of a phosphoric acid ester of a higher molecular weight alkyl or acyl derivative of a polyhydroxy substance, and heating the resulting mixture under reduced pressure at edible oil deodorization temperatures to remove volatile constituents, the percentage of said phosphoric acid being based on the weight of the oil.

29. The method of improving soya bean oil, particularly with respect to extending its prereversion period, which comprises mixing said oil with between about 0.0005% and 0.5%, based on the weight of the oil, of a phosphoric acid ester of a higher molecular weight alkyl or acyl derivative of a polyhydroxy substance, and. heating the resulting mixture, under reduced pressure, at a temperature between about 400 and 500 F. to remove volatile constituents.

The method of improving soya bean oil, particularly with respect to extending its prereversion period, which comprises mixing said oil with between about 0.0005% and 0.5%, based on the weight of the oil, of a phosphoric acid ester of a higher fatty acid monoglyceride or diglycer isle, and heating the resulting mixture, under reduced pressure in the presence of super-heated steam at edible oil deodorization temperatures to remove volatile constituents.

31. Soya bean oil, having improved color and a substantially extended pro-reversion period, comprising the reaction product, under reduced pressure and at steam deodorization temperatures, of soya bean oil and not substantially in excess of .5%,based on the weight of the oil, of a phosphoric acid ester of a higher molecular weight alkyl or acyl derivative of a polyhydroxy substance.

32.-The product of claim 31 wherein the ester is a phosphoric acid ester of a higher fatty acid monoglyceride or diglyceride.

33. The product of claim 31 wherein the soya bean oil is at least partially hydrogenated.

34. In a method of improving soya bean oil, particularly with respect to extending its prereversion period, the steps which include mixing said oil. with from about 0.005% to 0.5% of a phosphoric acid ester, based on the weight of the oil, and heating the resulting mixture in a substantially non-oxidizing atmosphere at a temperature of the order of about 400 F. to 500 F. for a substantial period of time.

K. EPSTEIN. 

